CN104833767A - Preparation method and application of GR/WS2-AuNPs-WS2 compound molecular imprinting sensor - Google Patents
Preparation method and application of GR/WS2-AuNPs-WS2 compound molecular imprinting sensor Download PDFInfo
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Abstract
The invention discloses a preparation method of a GR/WS2-AuNPs-WS2 compound molecular imprinting sensor. The preparation method includes the steps: 1) preparing tungsten sulfide which is nanosheet transition metal; 2) preparing an AuNPs/WS2 compound; 3) preparing a GR/WS2-AuNPs-WS2 compound; 3) preparing a GR/WS2-AuNPs-WS2 compound modified electrode; 4) taking the GR/WS2-AuNPs-WS2 compound as a substrate of the modified electrode, L-phenylalanine as a template molecule, 2-ethyl-4-methylimidazole as a crosslinking agent and methacrylic acid as a functional monomer to prepare an L-phenylalanine molecular imprinting sensor. The invention further provides an application of the molecular imprinting sensor in detection and separation of L-phenylalanine. L-phenylalanine detection sensitivity of the sensor is greatly improved owing to the GR/WS2-AuNPs-WS2 compound, and the prepared L-phenylalanine molecular imprinting sensor is high in L-phenylalanine sensitivity and selectivity by taking advantages of molecular imprinting.
Description
Technical field
The present invention relates to chemistry and the crossing domain of material, be specifically related to a kind of GR/WS
2-AuNPs-WS
2the preparation method of complex molecule trace sensor and application.
Background technology
Phenylalanine is one of essential amino acid, and what in human body, have physiological action only has L-type, therefore carries out detecting to the content synthesizing L-Phe in obtained DL-phenylalanine and split significant.The method of at present conventional detection phenylalanine has fluorescence method, high performance liquid chromatography, gas chromatography-mass spectrography etc., above method fast, efficient, but have that cost is high simultaneously, complicated operation, the shortcomings such as two kinds of enantiomorphs can not be identified.Electrochemical detection method instrument and equipment is simple, simple operation, molecular imprinting especially wherein, because it has good preparation precordainment and single-minded selectivity, the detection being applied to DL-phenylalanine be separated.But there is the shortcoming of poor sensitivity in the detection of existing molecular imprinting to phenylalanine, the sensitivity therefore improving molecular engram is significant.
Tungsten disulfide WS
2be a kind of transient metal sulfide with layer structure, between two sulphur layers, clip a metal tungsten layer, form the sandwich construction of similar sandwich-like, each metallic atom and six element sulphur Cheng Jian, form prism coordination model.Being connected by weak Van der Waals force between layers of this two-dimensional layer compound, connected by strong covalent bond between the S-W-S atom of interlayer, in layer, acting force is comparatively strong, and interlayer is relatively weak, therefore can introduce external molecule or atom by intercalation at interlayer.WS
2have many premium properties, as specific surface area is large, high adsorption capacity, reactivity is high, and catalytic performance is strong.
Golden nanometer particle AuNPs has special physical and chemical performance, as fluorescent characteristic, supermolecule and molecular recognition properties and catalytic activity etc., it is made to have extremely wide application prospect in biology sensor, photochemistry and the field such as electrochemical catalysis, optoelectronic device.Combined closely by electro-chemical attraction and golden sulfide linkage between the sulphur atom on tungsten disulfide surface and golden nanometer particle, gold nano-material is incorporated in curing tungsten layer, greatly can improve the catalytic performance of tungsten disulfide.
Graphene GR has a lot of good characteristic in electricity, optics, mechanics and thermal property etc., and especially its high specific surface area, good electric conductivity etc. make it in electricity and chemical hydridization device, have very large potential application.By GR and WS
2-AuNPs-WS
2compound substance combines, and greatly can improve specific surface area and the conductive capability of material.
In conjunction with the advantage of three kinds of materials, make the GR/WS prepared
2-AuNPs-WS
2compound substance has good electrochemical catalysis activity, large specific surface area and good electric conductivity, it is combined with molecular engram, greatly can improve the sensitivity detected L-Phe.Template molecule is done with L-Phe, 2-ethyl-4-methylimidazole makees crosslinking chemical, methacrylic acid does function monomer, the potassium ferricyanide does reaction amboceptor, molecular engram is prepared on the composite by cyclic voltammetry electropolymerization, hole size, the structure of this trace are identical with L-Phe, have special selectivity to it.React the change of right redox peak by the potassium ferricyanide, obtain template molecule and marking hole in conjunction with situation, and template molecule is detected and is separated, the GR/WS of preparation
2-AuNPs-WS
2complex molecule trace sensor has high detection sensitivity and single-minded selectivity to L-Phe.So far, relevant preparation GR/WS
2-AuNPs-WS
2compound substance is also applied to molecular engram and detects the report that the research of L-Phe not yet has domestic and foreign literature and Patents.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of GR/WS
2-AuNPs-WS
2the preparation method of complex molecule trace sensor, the method has the features such as preparation process is few, mild condition, and its molecular engram sensor has that specific surface area is large, conductive capability is strong, and selectivity is single-minded, sensitivity high.
Present invention also offers a kind of GR/WS
2-AuNPs-WS
2complex molecule trace sensor.
Present invention also offers GR/WS
2-AuNPs-WS
2the application of complex molecule trace sensor in the detection of L-Phe.
The present invention is achieved by the following technical solutions:
A kind of GR/WS
2-AuNPs-WS
2the preparation method of complex molecule trace sensor, comprises the following steps:
1) 1 ~ 1.5g sodium tungstate is got, 1.2 ~ 2g thioacetamide, add in 30ml intermediate water and mix, stir 2 ~ 3h, then in 180 ~ 200 DEG C of reaction 24 ~ 36h, after taking-up, naturally cool to room temperature, 5000 ~ 8000r/min centrifuging, use distilled water and absolute ethanol washing 3 ~ 5 times successively, under 55 ~ 70 DEG C of conditions, dry 12 ~ 18h, obtains nanoscale twins transition metal tungsten disulfide;
2) by 0.1 ~ 0.5g step 1) in nanoscale twins transition metal tungsten disulfide, and the gold chloride of 0.2 ~ 0.4mL 10mg/ml and 0.4 ~ 0.6g sodium borohydride join in 200ml intermediate water and mix to obtain mixed liquor; Measure 2.5 ~ 3.5ml mass concentration be 25% ~ 28% ammoniacal liquor add in mixed liquor, sonic oscillation 30 ~ 60min, 60 ~ 70 DEG C of Water Unders bathe heating 3 ~ 5 hours, be cooled to room temperature, leave standstill, suction filtration, get filter cake,-60 ~-45 DEG C of vacuum freeze dryings 12 ~ 24 hours, obtain a kind of tungsten disulfide lamella compound being attached with golden nanometer particle, i.e. AuNPs/WS
2compound;
3) get step 2) in compound 30 ~ 50mg be placed in 40 ~ 60ml methylene formamide solution, mix, add 20 ~ 30mg step 1) in obtained tungsten disulfide mixing, leave standstill reaction 1.5 ~ 3h, obtain WS
2-AuNPs-WS
2compound; Add 10 ~ 20mg Graphene again, ultrasonic 20 ~ 30min mixes, 40 ~ 60 DEG C of heating water bath 2 ~ 3h, and the product 8000 ~ 10000r/min centrifuging obtained, intermediate water cyclic washing 3 ~ 5 times, obtains GR/WS
2-AuNPs-WS
2compound;
4) 1 ~ 2mg step 3 is got) compound that obtains is in 1 ~ 2ml intermediate water, and ultrasonic 30 ~ 60min, obtains the uniform dispersion of compound, gets 5 ~ 7 μ l homogeneous dispersion and drips and be coated onto glassy carbon electrode surface, dry, obtains GR/WS
2-AuNPs-WS
2compound modified electrode;
5) the L-Phe mother liquor measuring 5 ~ 10ml 0.01mol/L joins in volumetric flask, adds 0.0330 ~ 0.0990g methacrylic acid successively, 0.1320 ~ 0.4950g 2-ethyl-4 methylimidazole, obtained electropolymerization solution; By GR/WS
2-AuNPs-WS
2compound modified electrode is placed in electropolymerization solution, and cyclic voltammetry is at voltage range-0.2 ~ 0.6V, and sweep speed 50 ~ 100mV/s, under scanning hop count 20 ~ 30 circle condition, carries out electropolymerization; The electrode be polymerized is placed in 0.5M NaOH solution, and cyclic voltammetry is at voltage range-0.2 ~ 0.6V, and sweep speed 50 ~ 100mV/s, by template molecule elution under scanning hop count 20 ~ 30 circle condition, obtains based on GR/WS
2-AuNPs-WS
2the L-Phe molecular engram sensor of compound.
Above-mentioned molecular engram sensor is used for the detection of L-Phe, comprises the following steps:
(1) standard solution preparation: the L-Phe standard solution preparing one group of gradient concentration, end liquid is the phosphate buffered solution of pH 7.4;
(2) working curve is drawn: L-Phe molecular engram electrode is placed in (1) Plays solution and leaves standstill 300 ~ 700s, take mercurous chloride electrode as contrast electrode, platinum electrode is auxiliary electrode, electrode prepared by the present invention is working electrode composition three-electrode system, then three-electrode system is placed in 5mM potassium ferricyanide solution, at K
3[Fe (CN)
6] in solution, adopt cyclic voltammetry to detect in voltage-0.2 ~ 0.6V, sweep speed 50 ~ 100mV/s, by detecting K
3[Fe (CN)
6] redox signal obtain detecting the linear equation of L-Phe, drawing curve;
(3) detection of L-Phe: replace the L-Phe standard solution in step (1) with testing sample, detect according to the method for step (2), according to response current value and working curve, obtain the content of L-Phe in testing sample.
Above-mentioned molecular engram sensor is used for the separation of L-Phe, comprises the following steps:
Take mercurous chloride electrode as contrast electrode, platinum electrode is auxiliary electrode, electrode prepared by the present invention is working electrode composition three-electrode system, first working electrode is placed in testing sample enrichment, then above-mentioned three-electrode system is placed in 0.5M NaOH solution, adopt cyclic voltammetry to carry out wash-out in voltage-0.2 ~ 0.6V, sweep speed 50 ~ 100mV/s, L-Phe molecule by wash-out out, is separated.
The beneficial effect of the application is:
(1) WS
2, AuNPs and GR tri-kinds of materials advantage combine, make prepare GR/WS
2-AuNPs-WS
2compound substance has good electrochemical catalysis activity, large specific surface area and good electric conductivity.
(2) the present invention's Graphene, sodium tungstate, thioacetamide and gold chloride are raw material, adopt one pot of reducing process, the GR/WS of synthesis
2-AuNPs-WS
2composite nano materials is also used successfully to modified electrode, and preparation technology is simple, and mild condition, productive rate is high.
(3) WS
2-AuNPs-WS
2compound has unique structure, this compound substance is made can effectively to improve electron transport rate and sensitivity, in the present invention, because tungsten disulfide lamella is made up of three layers of atomic layer, middle one deck is tungsten atom, two-layerly up and down be sulphur atom layer, with gold chloride course of reaction, sodium borohydride makees reductive agent, and gold chloride is reduced to golden nanometer particle, form golden sulfide linkage between golden nanometer particle and sulphur atom, make golden nanometer particle evenly be attached to tungsten disulfide sheet surfaces; By WS
2-AuNPs compound dispersion liquid and WS
2continue reaction, golden sulfide linkage is formed again, obtains WS
2-AuNPs-WS
2compound; The π key that Graphene is large and WS
2there is interaction in the electronic structure on surface, makes formation compound substance GR/WS
2-AuNPs-WS
2there is unique structure.
(4) the sensor of the present invention highly sensitive detection that successfully achieves L-Phe be separated, linear relationship Ip (μ A)=25.66+2.87logC (mol/L), R=0.9998, the concentration of L-Phe is 1.0 × 10
-7~ 1.0 × 10
-11in good linear relationship within the scope of mol/L, detect and be limited to 2.1 × 10
-12mol/L.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of molecular engram sensor of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1: a kind of GR/WS
2-AuNPs-WS
2the preparation method of complex molecule trace sensor, as shown in Figure 1, comprises the following steps:
(1) 1g sodium tungstate is got, 1.2g thioacetamide, add in 30ml intermediate water and mix, magnetic stirrer 2h, then proceed in 50mL stainless steel cauldron, in 180 DEG C of reaction 36h, naturally cool to room temperature after taking-up, 5000r/min centrifuging, use distilled water and absolute ethanol washing 3 times successively, dry 12h under 60 DEG C of conditions, prepares nanoscale twins transition metal tungsten disulfide;
(2) tungsten disulfide prepared by 0.1g step (1) is got, 0.2mL 10mg/ml gold chloride, 0.5g sodium borohydride, be dissolved in intermediate water, add the ammoniacal liquor that 3mL massfraction is 25% in fuming cupboard, sonic oscillation 30s, 60 DEG C of Water Unders bathe heating 3.5 hours, be cooled to room temperature, leave standstill, suction filtration, gets filter cake,-50 DEG C of vacuum drying 12 hours, obtain AuNPs/WS
2compound;
(3) AuNPs/WS is got
2compound 30mg is placed in 50ml methylene formamide solution, mixes, and adds 20mg tungsten disulfide, mixing, leaves standstill reaction 2h, obtains WS
2/ AuNPs/WS
2compound; Add 10mg Graphene again, ultrasonic disperse 20min, 50 DEG C of heating water bath 2h, leave standstill room temperature, 8000r/min centrifuging, and intermediate water washs 3 times, obtains GR/WS
2-AuNPs-WS
2compound;
(4) 2mg GR/WS is got
2-AuNPs-WS
2compound is dissolved in 2ml intermediate water, and liquid-transfering gun pipettes 7 μ l and evenly drips and be coated onto electrode surface, obtains GR/WS
2-AuNPs-WS
2compound modified electrode;
(5) the L-Phe mother liquor measuring 5ml 0.01mol/L joins in reaction bulb, adds 0.0530g methacrylic acid successively, 0.2320g 2-ethyl-4 methylimidazole, obtained electropolymerization solution; By GR/WS
2-AuNPs-WS
2compound modified electrode is placed in electropolymerization solution, cyclic voltammetry is at voltage range-0.2 ~ 0.6V, sweep speed 50mV/s, under scanning hop count 20 circle condition, carry out electropolymerization, the electrode be polymerized is placed in 0.5M NaOH solution, cyclic voltammetry is at voltage range-0.2 ~ 0.6V, sweep speed 50 ~ 100mV/s, by template molecule elution under scanning hop count 20 ~ 30 circle condition, obtains based on GR/WS
2-AuNPs-WS
2the L-Phe molecular engram sensor of compound.
Embodiment 2: a kind of GR/WS
2-AuNPs-WS
2the preparation method of complex molecule trace sensor, comprises the following steps:
(1) 1.2g sodium tungstate is got, 1.5g thioacetamide, add in 30ml intermediate water and mix, magnetic stirrer 2h, then proceed in 50mL stainless steel cauldron, in 200 DEG C of reaction 24h, naturally cool to room temperature after taking-up, 5000r/min centrifuging, use distilled water and absolute ethanol washing 4 times successively, dry 12h under 60 DEG C of conditions, prepares nanoscale twins transition metal tungsten disulfide;
(2) 0.2g tungsten disulfide is got, 0.3mL 10mg/ml gold chloride, 0.5g sodium borohydride, be dissolved in intermediate water, add the ammoniacal liquor that 3mL massfraction is 27% in fuming cupboard, sonic oscillation 50s, 60 DEG C of Water Unders bathe heating 3.5 hours, be cooled to room temperature, leave standstill, suction filtration, gets filter cake,-60 DEG C of vacuum drying 12 hours, obtain AuNPs/WS
2compound;
(3) get compound 40mg and be placed in 50ml methylene formamide solution, mix, add 20mg tungsten disulfide, mixing, leave standstill reaction 2h, obtain WS
2/ AuNPs/WS
2compound; Add 15mg Graphene again, ultrasonic disperse 30min, 50 DEG C of heating water bath 2h, leave standstill room temperature, 8000r/min centrifuging, and intermediate water washs three times, obtains GR/WS
2-AuNPs-WS
2compound;
(4) 1mg GR/WS is got
2-AuNPs-WS
2compound is dissolved in 2ml intermediate water, and liquid-transfering gun pipettes 7 μ l and evenly drips and be coated onto electrode surface, obtains GR/WS
2-AuNPs-WS
2compound modified electrode;
(5) the L-Phe mother liquor measuring 10ml 0.01mol/L joins in volumetric flask, adds 0.0730g methacrylic acid successively, 0.2320g 2-ethyl-4 methylimidazole, obtained electropolymerization solution; By GR/WS
2-AuNPs-WS
2compound modified electrode is placed in electropolymerization solution, cyclic voltammetry is at voltage range-0.2 ~ 0.6V, sweep speed 75mV/s, under scanning hop count 25 circle condition, carry out electropolymerization, the electrode be polymerized is placed in 0.5M NaOH solution, cyclic voltammetry is at voltage range-0.2 ~ 0.6V, sweep speed 50 ~ 100mV/s, by template molecule elution under scanning hop count 20 ~ 30 circle condition, obtains based on GR/WS
2-AuNPs-WS
2the L-Phe molecular engram sensor of compound.
Embodiment 3:
A kind of GR/WS
2-AuNPs-WS
2the preparation method of complex molecule trace sensor, comprises the following steps:
(1) 1.5g sodium tungstate is got, 2.0g thioacetamide, add in 30ml intermediate water and mix, magnetic stirrer 2h, then proceed in 50mL stainless steel cauldron, in 200 DEG C of reaction 36h, naturally cool to room temperature after taking-up, 5000r/min centrifuging, use distilled water and absolute ethanol washing 5 times successively, dry 12h under 65 DEG C of conditions, prepares nanoscale twins transition metal tungsten disulfide;
(2) 0.1g tungsten disulfide is got, 0.2mL 10mg/ml gold chloride, 0.6g sodium borohydride, be dissolved in intermediate water, add the ammoniacal liquor that 4mL massfraction is 28% in fuming cupboard, sonic oscillation 30s, 60 DEG C of Water Unders bathe heating 3.5 hours, be cooled to room temperature, leave standstill, suction filtration, gets filter cake,-45 DEG C of vacuum drying 12 hours, obtain AuNPs/WS
2compound;
(3) AuNPs/WS is got
2compound 20mg is placed in 50ml methylene formamide solution, mixes, and adds 20mg tungsten disulfide, mixing, leaves standstill reaction 2h, obtains WS
2/ AuNPs/WS
2compound; Add 10mg Graphene again, ultrasonic disperse 20min, 50 DEG C of heating water bath 2h, leave standstill room temperature, 8000r/min centrifuging, and intermediate water washs three times, obtains GR/WS
2-AuNPs-WS
2compound;
(4) 1mg GR/WS is got
2-AuNPs-WS
2compound is dissolved in 2ml intermediate water, and liquid-transfering gun pipettes 5 μ l and evenly drips and be coated onto electrode surface, obtains GR/WS
2-AuNPs-WS
2compound modified electrode;
(5) the L-Phe mother liquor measuring 10ml 0.01mol/L joins in volumetric flask, adds 0.0930g methacrylic acid successively, 0.4320g 2-ethyl-4 methylimidazole, obtained electropolymerization solution; By GR/WS
2-AuNPs-WS
2compound modified electrode is placed in electropolymerization solution, cyclic voltammetry is at voltage range-0.2 ~ 0.6V, sweep speed 100mV/s, under scanning hop count 30 circle condition, carry out electropolymerization, the electrode be polymerized is placed in 0.5M NaOH solution, cyclic voltammetry is at voltage range-0.2 ~ 0.6V, sweep speed 50 ~ 100mV/s, by template molecule elution under scanning hop count 20 ~ 30 circle condition, obtains based on GR/WS
2-AuNPs-WS
2the L-Phe molecular engram sensor of compound.
Embodiment 4: prepared by above-described embodiment 1-3 based on GR/WS
2-AuNPs-WS
2the L-Phe molecular engram sensor of compound, for the detection of L-Phe, step is as follows:
(1) standard solution preparation: the L-Phe standard solution preparing one group of gradient concentration, end liquid is the phosphate buffered solution of pH 7.4;
(2) working curve is drawn: L-Phe molecular engram electrode is placed in (1) Plays solution and leaves standstill 300 ~ 700s, take mercurous chloride electrode as contrast electrode, platinum electrode is auxiliary electrode, electrode prepared by the present invention is working electrode composition three-electrode system, then three-electrode system is placed in 5mM potassium ferricyanide solution, at K
3[Fe (CN)
6] in solution, adopt cyclic voltammetry to detect in voltage-0.2 ~ 0.6V, sweep speed 50 ~ 100mV/s, by detecting K
3[Fe (CN)
6] redox signal obtain detecting the linear equation of L-Phe, drawing curve;
(3) detection of L-Phe: replace the L-Phe standard solution in step (1) with testing sample, detect according to the method for step (2), according to response current value and working curve, obtain the content of L-Phe in testing sample.
The concentration of L-Phe is 1.0 × 10
-7~ 1.0 × 10
-11in good linear relationship within the scope of mol/L, detect and be limited to 2.1 × 10
-12mol/L.
Embodiment 5: prepared by above-described embodiment 1-3 based on GR/WS
2-AuNPs-WS
2the L-Phe molecular engram sensor of compound, for the separation of L-Phe, step is as follows:
In the solution molecular engram sensor of preparation being placed in DL-phenylalanine 10 minutes, based on the effect of trace, only has L-Phe by enrichment; Take mercurous chloride electrode as contrast electrode, platinum electrode is auxiliary electrode, the trace sensor being enriched L-Phe is working electrode composition three-electrode system, above-mentioned three-electrode system is placed in 0.5M NaOH solution, cyclic voltammetry is adopted to carry out wash-out in voltage-0.2 ~ 0.6V, sweep speed 50 ~ 100mV/s, L-Phe molecule by wash-out out, is separated.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a GR/WS
2-AuNPs-WS
2the preparation method of complex molecule trace sensor, is characterized in that, comprise the following steps:
1) get sodium tungstate and thioacetamide mixes in intermediate water, then in 180 ~ 200 DEG C of reactions, be cooled to room temperature after taking-up, wash after centrifuging, dry, obtain nanoscale twins transition metal tungsten disulfide;
2) by step 1) in nanoscale twins transition metal tungsten disulfide, and gold chloride and sodium borohydride join in intermediate water and mix, and obtain mixed liquor; Added by ammoniacal liquor in mixed liquor, after vibration, heating, is cooled to room temperature, and leave standstill, suction filtration, gets filter cake, vacuum freeze drying, obtains a kind of tungsten disulfide lamella compound being attached with golden nanometer particle, i.e. AuNPs/WS
2compound;
3) get step 2) obtained compound is placed in methylene formamide solution, mix, add step 1) in obtained tungsten disulfide mixing, leave standstill reaction, obtain WS
2-AuNPs-WS
2compound; Add Graphene again, mix rear heating, by the product centrifuging obtained, washing, obtains GR/WS
2-AuNPs-WS
2compound;
4) step 3 is got) GR/WS that obtains
2-AuNPs-WS
2compound is dissolved in intermediate water, obtains the uniform dispersion of compound; Get above-mentioned homogeneous dispersion to drip and be coated onto glassy carbon electrode surface, dry, obtain GR/WS
2-AuNPs-WS
2compound modified electrode;
5) prepare L-Phe mother liquor, add methacrylic acid and 2-ethyl-4 methylimidazole successively, obtained electropolymerization solution; By GR/WS
2-AuNPs-WS
2compound modified electrode is placed in electropolymerization solution, and cyclic voltammetry carries out electropolymerization; Electrode after polymerization is placed in 0.5M NaOH solution, and cyclic voltammetry scanning, by template molecule elution, obtains based on GR/WS
2-AuNPs-WS
2the L-Phe molecular engram sensor of compound.
2. a kind of GR/WS as claimed in claim 1
2-AuNPs-WS
2the preparation method of complex molecule trace sensor, is characterized in that, comprise the following steps:
1) 1 ~ 1.5g sodium tungstate is got, 1.2 ~ 2g thioacetamide, add in 30ml intermediate water and mix, stir 2 ~ 3h, then in 180 ~ 200 DEG C of reaction 24 ~ 36h, after taking-up, naturally cool to room temperature, 5000 ~ 8000r/min centrifuging, use distilled water and absolute ethanol washing 3 ~ 5 times successively, under 55 ~ 70 DEG C of conditions, dry 12 ~ 18h, obtains nanoscale twins transition metal tungsten disulfide;
2) by 0.1 ~ 0.5g step 1) in nanoscale twins transition metal tungsten disulfide, and the gold chloride of 0.2 ~ 0.4mL 10mg/ml and 0.4 ~ 0.6g sodium borohydride join in 200ml intermediate water and mix to obtain mixed liquor; Measuring 2.5 ~ 3.5ml ammoniacal liquor adds in mixed liquor, sonic oscillation 30 ~ 60min, and heating water bath 3 ~ 5 hours, is cooled to room temperature, leave standstill, suction filtration, gets filter cake, vacuum freeze drying 12 ~ 24 hours, obtains a kind of tungsten disulfide lamella compound being attached with golden nanometer particle, i.e. AuNPs/WS
2compound;
3) get step 2) in compound 30 ~ 50mg be placed in 40 ~ 60ml methylene formamide solution, mix, add 20 ~ 30mg step 1) in obtained tungsten disulfide mixing, leave standstill reaction 1.5 ~ 3h, obtain WS
2-AuNPs-WS
2compound; Add 10 ~ 20mg Graphene again, ultrasonic 20 ~ 30min mixes, heating water bath 2 ~ 3h, and the product 8000 ~ 10000r/min centrifuging obtained, intermediate water cyclic washing 3 ~ 5 times, obtains GR/WS
2-AuNPs-WS
2compound;
4) 1 ~ 2mg step 3 is got) GR/WS that obtains
2-AuNPs-WS
2compound is in 1 ~ 2ml intermediate water, and ultrasonic 30 ~ 60min, obtains the uniform dispersion of compound, gets the above-mentioned homogeneous dispersion of 5 ~ 7 μ l and drips and be coated onto glassy carbon electrode surface, dry, obtains GR/WS
2-AuNPs-WS
2the electrode that compound is modified;
5) the L-Phe mother liquor measuring 5 ~ 10ml 0.01mol/L joins in volumetric flask, adds 0.0330 ~ 0.0990g methacrylic acid successively, 0.1320 ~ 0.4950g 2-ethyl-4 methylimidazole, obtained electropolymerization solution; By GR/WS
2-AuNPs-WS
2compound modified electrode is placed in electropolymerization solution, and cyclic voltammetry is at voltage range-0.2 ~ 0.6V, and sweep speed 50 ~ 100mV/s, under scanning hop count 20 ~ 30 circle condition, carries out electropolymerization; The electrode be polymerized is placed in 0.5M NaOH solution, and cyclic voltammetry is at voltage range-0.2 ~ 0.6V, and sweep speed 50 ~ 100mV/s, by template molecule elution under scanning hop count 20 ~ 30 circle condition, obtains based on GR/WS
2-AuNPs-WS
2the L-Phe molecular engram sensor of compound.
3. a kind of GR/WS as claimed in claim 2
2-AuNPs-WS
2the preparation method of complex molecule trace sensor, is characterized in that, described in step (2), the mass concentration of ammoniacal liquor is 25% ~ 28%.
4. a kind of GR/WS as claimed in claim 2
2-AuNPs-WS
2the preparation method of complex molecule trace sensor, is characterized in that, described in step (2), the temperature of water-bath is 60 ~ 70 DEG C.
5. a kind of GR/WS as claimed in claim 2
2-AuNPs-WS
2the preparation method of complex molecule trace sensor, is characterized in that, described in step (2), the temperature of vacuum freeze drying is-60 ~-45 DEG C.
6. a kind of GR/WS as claimed in claim 2
2-AuNPs-WS
2the preparation method of complex molecule trace sensor, is characterized in that, described in step (3), the temperature of water-bath is 40 ~ 60 DEG C.
7. a kind of Graphene/WS that as described in any one of claim 1-6 prepared by method
2-AuNPs-WS
2complex molecule trace sensor.
8. Graphene/WS as claimed in claim 7
2-AuNPs-WS
2complex molecule trace sensor is detecting the application of L-Phe, and it is characterized in that, detecting step comprises:
(1) standard solution preparation: the L-Phe standard solution preparing one group of gradient concentration, end liquid is the phosphate buffered solution of pH 7.4;
(2) working curve is drawn: the standard solution that L-Phe molecular engram sensor is placed in step (1) leaves standstill 300 ~ 700s; Take mercurous chloride electrode as contrast electrode, platinum electrode is auxiliary electrode, based on GR/WS
2-AuNPs-WS
2the L-Phe molecular engram sensor of compound is working electrode composition three-electrode system, then three-electrode system is placed in K
3[Fe (CN)
6] in solution, adopt cyclic voltammetry to detect in voltage-0.2 ~ 0.6V, sweep speed 50 ~ 100mV/s, by detecting K
3[Fe (CN)
6] redox signal obtain detecting the linear equation of L-Phe, drawing curve;
(3) detection of L-Phe: replace the L-Phe standard solution in step (1) with testing sample, detect according to the method for step (2), according to response current value and working curve, obtain the content of L-Phe in testing sample.
9. apply as claimed in claim 8, it is characterized in that, described K
3[Fe (CN)
6] concentration of solution is 5mmol/L.
10. Graphene/WS as claimed in claim 7
2-AuNPs-WS
2complex molecule trace sensor, in the application of separation of L-phenylalanine, is characterized in that, take mercurous chloride electrode as contrast electrode, and platinum electrode is auxiliary electrode, GR/WS
2-AuNPs-WS
2molecular engram sensor is working electrode composition three-electrode system, first working electrode is placed in testing sample enrichment, then above-mentioned three-electrode system is placed in 0.5M NaOH solution, cyclic voltammetry is adopted to carry out wash-out in voltage-0.2 ~ 0.6V, sweep speed 50 ~ 100mV/s, L-Phe molecule by wash-out out, is separated.
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